Substituted triazines

ABSTRACT

Triazines of the formula   WHEREIN X is halogen or alkylthio; R is hydrogen or alkyl; R1 and R2 are individually alkyl and R3 is aryl optionally substituted with halogen atoms, alkyl groups or alkoxy groups, are useful as herbicides.

United States Patent" [1 1 Brown, deceased [451 July 3,1973

[ SUBSTITUTED TRIAZINES [75 Inventor: Melancthon S. Brown, deceased, late of Berkeley, Calif. by Gustave K. Kohn, administrator [73] Assignee: Chevron Research Company, San

Francisco, Calif.

[22] Filed: May 12, 1971 [21] Appl. No.: 142,758

[52] US. Cl. 260/249.8, 71/93 [51] Int. Cl C07d 55/20 [58] Field of Search 260/249.8

[56] References Cited UNITED STATES PATENTS 3,l4l,885 7/1964 Ross et al. 260/249.8

Primary Examiner-John M. Ford Artorney.l. A. Buchanan, Jr.

[57] ABSTRACT Triazines of the formula alkoxy groups, are useful as herbicides.

10 Claims, No Drawings SUBSTITUTED TRIAZINES BACKGROUD OF THE INVENTION 1. Field The present invention is irected to 2,4,6-substituted methylamino--chloro-l,3,5-triazine, Z-(N-phenylthio- 1,3,5-triazines and their use as herbicides. More partic- N-methylamino)-4-dimethylamino-o-fluoro-l ,3,5- ularly, the present invention is directd to Z-(N-arylthiotriazine, 2-(N-4-chlorophenylthio-N-ethylamino)-4- N-alkylamino )-4-alkylamino-6-haloor -6-alkylthiomethylamino-6-chloro-1,3,5-triazine, 2-(N-4- 1,3 ,S-triazines. chlorophenylthio-N-ethylamino )-4-methylamino-6- 2. Prior Art 10 bromo-l,3,5-triazine, 2-(N-4-chlorophenylthio-N- Triazines and derivatives thereof are known to have ethylamino)-4-methylamino-6-fluoro-l,3,5-triazine, utility in a variety of areas such as fungicides and herbi- 2-(N-4chlorophenylthio-N-ethylamino)-4- cides. U.S. Pat. Nos. 2,891,855, 2,909,419 and isopropylamino-6-chloro-l,3,5-triazine, 2-(N-3,4- 2,907,763 disclose amino substituted triazines and dichlorophenylthio-N-methylamino)-4- their use as hericides. U.S. Pat. Nos. 3,079,391 and I5 methylethylamino-o-chloro-l,3,5-triazine, 2-(N-4- 3,138,445 disclose perchloromethylmercaptoamin methylphenylthio-N-n-butylamino )-4 -dimethylaminotriazines and their use as herbicides. 6-methylthio-l,3,5-triazine, 2-(N-4- methoxyphenylthio-N-isopropylamino)-4-t- DESCRIPTION OF THE INVENTION butylamino-6-chloro-l ,3,5-triazine, 2-(N-2-chloro-4- Compounds of the present invention may be repre- Z0 methylphenylthio-N-ethylamino)-4- sented by the formula methylisopropylamino-6-n-butylthio-l,3,5-triazine, 2- N (N-l-naphthylthio-N-methylamino)-4-methylamino-6- u o I\IS-R chloro- 1,3,5-triazine, etc.

Q I The compounds of the present invention are prepared by reacting a sulfenyl halide with an aminotriazinc in approximately equimolar amounts in the presence of a basic acceptor according to the following re- R R action a i B i X-G C Nl-I IHSCI C-N-SR 13-1101 l. I t l V o o .\'1 s R/ \R1 R/ Rl wherein X iS halogen of atomic number 9 IO (flUO- 40 wherein X, R, R! R and R3 are as defined above and rine, chlorine or bromine) or alkylthio of l to 4 carbon B represents a basic acceptor such as pyridine o i rh atoms; R is hydrogen or alkyl of l to 4 carbon atoms; ylamine. The amount of basic acceptor should be at R is alkyl of l to 4 carbon atoms; R is alkyl 0f 1 t0 4 least equal in moles to the sulfenyl chloride. Normally carbon atoms and R is aryl 0f 6 to 12 carb atoms the reaction is conducted in a polar watermiscible solsubstitued with 0 to 2 halogen atoms of atomic number v m su h as dimcth lfcrmamidc, acct nitril dimcth- 9 t0 alkyl g p of 1 t0 4 Carbon atoms alkoxy oxyethane or dimethyl sulfoxide. In such highly polar groups of l to 4 carbon atoms (the total number of subsolvents temperatures of 20 to 30 C. and reaction stituents is preferably 2). Preferably, R is phenyl subtimes of one-quarter to 10 hours are adequate for comstituted with 0 to 2 halogens of atomic number 9 to 35, pletion of the reaction. The product is isolated by addalkyl groups of l to 4 carbon atoms or alkoxy g ps ing a solvent not miscible with water, for example chloof l to 4 carbon atoms. rinated hydrocarbons such as methylene chloride or Preferably X is chlorine me hy R is y g n; chloroform, benzene, toluene, diethylethcr, etc. and R is alkyl of l to 3 carbon atoms; R is alkyl of l to 3 then water washing to remove the initial solvent and carbon atoms and R is phenyl substituted with 0 t0 1 the amine salt. The product can then be isolated further halogens of atomic number 9 t 5, p rly chloby addition of a nonpolar solvent such as hexane or by rine. More preferably R and R, are the sameevaporation to dryness. The crude product can be puri- Represenaative alkylthio groups which X may reprefi d b recrystallization or h mat h sent include methylthio, ethylthio, isopropylthio, nwh n the aminotriazine reactant has R as H, nd R propylthio, n-butylthio, sec.butylthio, etc. and R as different alkyl groups, a mixture of products Representative alkyl groups which R, R and R may is obtained. Separation is generally accomplished by represent include methyl, ethyl, n-propyl, isopropyl, crystallization or chromato r h n-butyl, t-butyl, sec.butyl, etc. Alternately, the compounds of the present invention Representative aryl groups which R m y repr can be prepared by conducting the reaction indicated include phenyl, naphthyl, 4-chlorophenyl, 4- above in the presence of a less polar solvent such as bromophenyl, 4-fluorophenyl, 3,4-dichlorophenyl, 2,4- dichlorophenyl, 3,5-difluorophenyl, 4-methylphenyl, 4-ethylpheny], 2-chloro-4-methylphenyl, 4-

2 methoxyphenyl, 4-butoxyphenyl, 2,4- dimethoxyphenyl, etc.

Representative compounds of the present invention include 2-( N-phenylthio-N -methylamino )-4- benzene or toluene in the presence of a tertiary amine such as 2,6-lutidine, collidine, pyridine or triethylamine. When using these solvents, such as benzene or toluene, higher reaction temperatures and longer reaction times will generally be desirable. A temperature of 50 C. up to the boiling point of the solvent will gener TABLE 1 Elemental analysis, percent.

, Sulfur Chlorine Moll;- ally be employed. When the reaction is complete, the 135a? anew point amine salt and the unreacted triazine may be removed 5 C(nnpound med pound med Found by filtration and any residual amine salt washed out (NphenylthigNgthyL with water. The product may then be isolated by evapoa i m l ehylnmi o-fi- 33 O I) 1 r ,3 rating to dryness or concentrating and precipitating f ifgfi gg gmfYfggij' with a less polar solvent such as hexane. The product gg i ggfi igfiih gh may be purified by recrystallization or by digesting in triazine 8.06 8.93 10.75 19.73 02400 a nonpolar solvent such as hexane. UTILITY The Preseht invention can he more fully understood The triazines of the present invention are, in general, y reference to the following examples Showing the herbicidal in both preand post-emergence applica- Piepaiatioh of Select compouhds- The examples are hot tions. For preemergence control of undesirable vegetaconsidered limiting but are illustrative of the method of 15 tion these triazines will be applied in herbicidal m- Piepaiaiioh- Unless otherwise indicated Percentages ties to the environment, e.g., soil infested with seeds are by weight. Example 1 2-(N4-chlorophenylthio' and/or seedlings of such vegetation. Such application ethylamino)-4-ethy1amin-6-hir-13,54riazine will inhibit the growth of or kill the seeds, germinating 3- (0-08 mole) of 4chiorophenyisulfenyi ch10 seeds and seedlings. For post-emergence applications ride was Slowly added to mole) of 20 the triazines of the present invention will be applied dieihyiamiho'6'chioro'it3t5'triazihe and of W rectly to the foliage and other plant parts. Generally dine in 100 dimethyiioimamide at ambient temper they are effective against weed grasses as well as broadature.'The reaction mixture was stirred for 2 hours, dileaved weeds s may be Selective with respect to luted with 750 ml. diethyl ether, washed once with 500 type of application and/or f weed ml. water then twice with 250 ml. portions of water, foland p0st emerge'nce herbicidal tests on rePreiowed y drying Over magnesium Sulfate and fiitei'ingsentative triazines of this'invention were made using The solvent was removed under vacuum and the crude the following methods; crystalline product purified by chromatographing on a pre Emergence Test silica g column, ehitihg with eiher'hexahe- The P An acetone solution of the test triazines was prepared isoiated y chromatography w further Purified by by mixing 750 mg. triazine, 220 mg. of nonionic surfacrecrystallizing from benzene-hexane. The recrystallized mm and 25 of acetone This solution was added to material melted at 13l-5 C. and analyzed as follows: appmximately 5 ml. f water containing 15 f surfactant.

Seeds of the test vegetation were planted in a pot of Calculated Found soil and the triazine solution was sprayed uniformly S onto the soil surface at a dose of 100 mg. per cm. The Cl 20'7O pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for Example 2 p y 40 a 3-week period. At the end of this period the herbiisopropylami110) -isopropylamino-6-methylthiocidal effectiveness of the triazine was rated based on 1,3,5-triazine the physiological observations. A 0 to 100 scale was 33 gmole) of 4-chl0r0phenylsulfeny1 chloused; 0 representing no phytotoxicity, 100 representing ride was added slowly to 30 g. (0.124 mole) of 2,4-bisom let kill. isopropyl-methylthio-l,3,5-triazine and 20 g. of pyri- Post-Emergene T t dine in 150 dimethylf0mlamide- After being The test triazine was formulated in the same manner stirred for one hour the reaction mixture was diluted as d ib d above f h pre emorgenoe t t Th with ether washed with water, dried Over magnesium concentration of the triazine in this formulation was sulfate and filtered. The solvent was removed under 5 000 ppm Thi f l i was if l sprayed on vacuum and the crude Product chromatographed on a 2 replicate pots of 24-day-old'plants (approximately 15 column of silica gel, eluting with ether-hexane. 2-(N-4- to 25 l t r ut) at a dose of 100 mg. per cm. chlorophenylthio-4-isopropylamino)- After the plants had dried, they were placed in a greenp py y t3,5-trialine was YBCOV- house and then watered intermittently at their bases as ei'ed as an Analysis was as fohowsi needed. The plants were observed periodically for phytotoxic effects and physiological and morphological re- S fgg 2g; sponses to the treatment. After 3 weeks the herbicidal Cl 9.26 9.84 effectiveness of the triazine was rated based on these observations. A 0 to 100 scale was used; 0 representing Other compounds of the present invention were preno phytotoxicity, 100 representing complete kill.

pared and are tabulated in Table I. The results of these tests appear in Table ll.

TABLE II Com pound Herbicidal effectiveness, pro/post.

0 W C M 1 L 2-(N4-chloropl1cnylthio-Nothylamino)4-ctl1ylnmino-(l-chloro-l,3,5-lrialinc. 99/100 98/100 98/100 98/100 100/100 100/100 2-(N-4-chlorophcnylthioN-isopropylamino)-4-isopropylztmino-fi-motllyllhio-l,3,5-l rinzino. /100 /100 100/100 100/100 100/100 100/100 2-(N-phmiylthio-N-othylamino)-4-cthylamino-G-chloro-l,3,5triazinv 100/100 100/100 100/100 100/100 100/100 100/100 2-(N-4-chlorophnnylthio-N'cthylammo)--t-isopropylamino-fi-cliloro-l,3,5 traiZinv. 100/100 100/100 100/100 100/100 100/190 100/100 No'lE.O=WiId outs (Azmm fatua); W=Wutorgrttss (Echz'nuchlou crusgalli); (J=Crubgruss (Dig i/aria sanguinalis); M=Mustard (Brussim amen-sis); l=ln.:wnud (Amaranthus rctroflczua); L=Lambsquartor (Cllcnopadz'um album).

The amount of triazine administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application, i.e., sheltered areas such as greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pre-emergent control of most plants dosages in the range of about 0.5 to lbs. per acre will be used. Such administration will give a concentration of about 2 to 80 ppm. triazine distributed throughout 0.1 acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. triazine per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. triazine per acre.

The herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described triazines intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and gener ally enhance their effectiveness. These compositions may also contain other pesticides, stabilizers, conditioners, fillers and the like.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim: 1. Compound of the formula N R2 X-o o-r r-s-m Q I 7 N lt R wherein X is halogen of atomic number 9 to 35 or alkylthio of l to 4 carbon atoms; R is hydrogen or alkyl of l to 4 carbon atoms; R and R are individually alkyl of 1 to 4 carbon atoms; R is carbocyclic aryl of 6 to 12 carbon atoms substituted with 0 to 2 halogen atoms of atomic number 9 to 35, with O to 2 alkyl groups of l to 4 carbon atoms or with 0 to 2 alkoxy groups of l to 4 carbon atoms.

2. Compound of claim 1 wherein R is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 35, with 0 to 2 alkyl groups of l to 4 carbon atoms, or with 0 to 2 alkoxy groups of l to 4 carbon atoms.

3. Compound of claim 2 wherein R is phenyl substituted with 0 to l halogen atom of atomic number 9 to 35.

. 4. Compound of claim 2 wherein R is hydrogen.

5. Compound of claim 1 wherein X is chlorine or methylthio;R is hydrogen; R is alkyl of l to 3 carbon atoms; R is alkyl of l to 3 carbon atoms and R is phenyl or chlorophenyl.

6. Compound of claim 5 wherein R is phenyl or 4- chlorophenyl.

7. Compound of claim 6 being 2-(N-4- chlorophenylthio-N-ethylamino)-4-ethylamino-6- chloro l ,3 ,5-triazine.

8. Compound of claim 6 being 2-(N-4- chlorophenylthio-N-isopropylamino)-4- isopropylamino-fi-methylthio-l ,3 ,S-triazine.

9. Compound of claim 6 being Z-(N-phenylthio-N- ethylamino)-4-ethylamino-6-chloro-l ,3 ,S-triazine.

10. Compound of claim 6 being 2-(N-4- chlorophenylthio-N-ethylamino)-4-isopropylamino-6- chloro-l ,3,5-triazine. 

2. Compound of claim 1 wherein R3 is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 35, with 0 to 2 alkyl groups of 1 to 4 carbon atoms, or with 0 to 2 alkoxy groups of 1 to 4 carbon atoms.
 3. Compound of claim 2 wherein R3 is phenyl substituted with 0 to 1 halogen atom of atomic number 9 to
 35. 4. Compound of claim 2 wherein R is hydrogen.
 5. Compound of claim 1 wherein X is chlorine or methylthio; R is hydrogen; R1 is alkyl of 1 to 3 carbon atoms; R2 is alkyl of 1 to 3 carbon atoms and R3 is phenyl or chlorophenyl.
 6. Compound of claim 5 wherein R3 is phenyl or 4-chlorophenyl.
 7. Compound of claim 6 being 2-(N-4-chlorophenylthio-N-ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine.
 8. Compound of claim 6 being 2-(N-4-chlorophenylthio-N-isopropylamino)-4-isopropylamino-6-methylthio -1,3,5-triazine.
 9. Compound of claim 6 being 2-(N-phenylthio-N-ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine.
 10. Compound of claim 6 being 2-(N-4-chlorophenylthio-N-ethylamino)-4-isopropylamino-6-chloro-1,3,5 -triazine. 